EP2574599A1 - Container for storing ammonia by sorption - Google Patents

Container for storing ammonia by sorption Download PDF

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Publication number
EP2574599A1
EP2574599A1 EP11183413A EP11183413A EP2574599A1 EP 2574599 A1 EP2574599 A1 EP 2574599A1 EP 11183413 A EP11183413 A EP 11183413A EP 11183413 A EP11183413 A EP 11183413A EP 2574599 A1 EP2574599 A1 EP 2574599A1
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EP
European Patent Office
Prior art keywords
cells
tank according
ammonia
tank
sorption
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11183413A
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German (de)
French (fr)
Inventor
François Dougnier
Jules-Joseph Van Schaftingen
Pierre De Keyzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Plastic Omnium Advanced Innovation and Research SA
Original Assignee
Inergy Automotive Systems Research SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inergy Automotive Systems Research SA filed Critical Inergy Automotive Systems Research SA
Priority to EP11183413A priority Critical patent/EP2574599A1/en
Priority to CN201280050396.XA priority patent/CN103857624A/en
Priority to PCT/EP2012/069342 priority patent/WO2013045696A1/en
Priority to EP12778644.0A priority patent/EP2760792A1/en
Priority to US14/348,420 priority patent/US20140284224A1/en
Publication of EP2574599A1 publication Critical patent/EP2574599A1/en
Withdrawn legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/003—Storage or handling of ammonia
    • C01C1/006—Storage or handling of ammonia making use of solid ammonia storage materials, e.g. complex ammine salts

Definitions

  • the invention relates to a tank for the storage of ammonia by sorption, preferably by chemisorption on a solid.
  • SCR selective catalytic reduction
  • doses of ammonia are injected into the exhaust line upstream of a catalyst on which the reduction reactions take place.
  • ammonia is produced by thermal decomposition of a precursor, usually an aqueous solution of urea.
  • Embedded systems for storing, dispensing and dosing a standard urea solution such as that sold under the name Adblue®, a eutectic solution containing 32.5% urea in water have thus been placed on the market.
  • Requirement US 2010/0062296 proposes a chemisorption ammonia storage system involving at least two tanks or compartments of the same tank containing different absorbent materials and having different sizes, these reservoirs / compartments communicating to allow the passage of ammonia between them. Once the system is depleted of ammonia, the largest of these (usually the one that serves as a reserve for the smallest) is replaced.
  • the present invention aims to provide a storage tank for ammonia sorption, which is easy to manufacture, whose shape can easily be adapted to its environment on a vehicle and which can easily be recharged with ammonia instead of being replaced at least partially.
  • the invention relates to a tank for the storage of ammonia by sorption, said tank comprising cells communicating with each other and with at least one orifice communicating with the outside, these cells being able to contain a solid intended for the ammonia sorption.
  • reservoir is meant a container or enclosure defining at least one internal volume serving as a container for the solid.
  • the reservoir comprises at least one wall delimiting cavities, i.e. cavities capable of containing said solid. These cavities may have any shape. Preferably, they all have the same shape.
  • the solid is intended for the sorption (preferably chemisorption) of ammonia.
  • sorption preferably chemisorption
  • These are usually alkali metal, alkaline earth or transition metal chlorides.
  • These solids can be in the powdery state or in the form of agglomerates.
  • the shape and size of the cells are preferably adapted to fit at least a portion of the outer surface of the agglomerates.
  • the cells are made of plastic.
  • Thermoplastic materials give good results in the context of the invention, in particular because of the advantages of weight, mechanical and chemical resistance and easier implementation (which makes it possible to obtain complex shapes).
  • polyolefins polyvinyl halides
  • thermoplastic polyesters polyketones
  • polyamides polyphthalamides
  • a mixture of polymers or copolymers may also be used, as well as a mixture of polymeric materials with inorganic, organic and / or natural fillers such as, for example, but not limited to: carbon, salts and other inorganic derivatives, natural fibers, glass fibers and polymeric fibers.
  • multilayer structures consisting of stacked and solid layers comprising at least one of the polymers or copolymers described above.
  • the cells of the tank according to the invention may at least partly be made in one piece, for example in the form of plate (s) injected.
  • a bottom plate comprising sinusoid segments is assembled with a domed top plate.
  • the cells may be made separately (individually or in groups), for example by injection or blowing of plastic material, and then assembled by any known means, such as by welding, for example.
  • This variant makes it possible to perform a non-parallel assembly of the cells, ie. such that with cells of identical shape, at least one of the faces of said cells is not parallel to the similar face of its neighbor.
  • the production of groups of cells by injection is particularly advantageous because it makes it possible in particular to economically produce very small cells.
  • the small cells allow to obtain a good resistance of these to the (de) internal pressure, and improve the heat exchange between the heating and / or cooling systems and the reagent.
  • the cells communicate with each other so as to ensure the circulation of ammonia both during the filling (refilling) of the reservoir and during its use (consumption or discharge of ammonia).
  • This communication is generally provided by at least one orifice in each cell and by a device connecting these orifices to each other and to at least one orifice communicating with the outside of the tank, so as to allow its recharging and discharge ammonia.
  • all the cells or a subgroup of them is surmounted by a network of pipes providing communication between them.
  • a network of pipes providing communication between them.
  • said network also generally performs a role of mechanical reinforcement, increasing the mechanical resistance and resistance to (de) pressure of the reservoir.
  • the network may be free but preferably it is secured to a cover covering the cells and playing a role of additional reinforcement.
  • the cells are grouped together under a common lid, delimiting with their upper face a hollow volume and each cell comprises at least one orifice communicating with this volume, the lid comprising at least one orifice ensuring the communication of this volume with the outside of the tank.
  • the cover may also serve to assemble the cells (to make them mechanically integral) and / or to reinforce the reservoir.
  • the shape of the cells (all or part of them) and / or their embodiment and / or assembly is such that at least one active element of the system (fulfilling a useful function such as heating, cooling or mechanical reinforcement) can be inserted into or between them.
  • a heating element or a phase change material (MCP, or material storing or returning heat by changing phase according to the surrounding temperature) is advantageously inserted in or between the cells.
  • heating elements or phase change materials makes it possible to stabilize the temperature of the reagent contained in the cell and thus ensure a stable production of ammonia.
  • the use of differentiated heating between cells and / or different relative amounts of phase change materials between cells allows to deplete or enrich some cells to ammonia; for example, during a shutdown of the system (following for example a stopping of the vehicle), the ammonia load in the cells cooling faster (containing for example little or no phase change material) will increase to the detriment of the cells cooling more slowly (containing for example a lot of phase change material). This may be particularly advantageous to ensure rapid availability of ammonia after stopping the vehicle, for example by activating at this time preferably ammonia-rich cells.
  • the cells may also be traversed or penetrated, preferably in their largest dimension, by one or more channels optionally closed at one of their ends and which also allows the insertion of an active element of the system.
  • This arrangement is particularly favorable for the positioning of heating or cooling means: the channels being placed substantially in the center of the reagent allow rapid heat exchange.
  • the heating or cooling means which are positioned therein must not be attached tightly. This makes it possible in particular to dismount them easily, and to alternately mount in these channels heating means (during the desorption of ammonia) or cooling (during the absorption of ammonia).
  • the heating means and / or MCP, as well as the cooling means can be placed both in internal channels and outside the cells, or even with regard to the MCP inside the cells, in the chamber reagent.
  • a particularly interesting combination is to place the heating means in channels as described above and the MCP outside the cells, possibly topped with isolation means; this configuration makes it possible to obtain good dynamic performance of the heating system: when starting in cold conditions, the heat generated inside the channels is indeed very quickly transmitted to the reagent, because the enthalpy needed to the heating of the channels is weak because of their small dimensions and their small masses.
  • the MCPs placed outside the cells do not start heating until the reagent bed is heated and allow the heat to be recovered at the periphery and to stabilize the reagent temperature and the ammonia pressure. Outdoor PCMs also have an insulating effect, complementary to that of insulators that can be placed in an outer layer above PCMs.
  • the reservoir comprises a MCP in at least a portion of the cells and / or between at least part of them and / or in an insulating channel of at least a part of they.
  • the walls of the cells may be provided with internal ribs allowing good gas passage between the reagents and the walls. This passage also limits heat loss to the outside of the device.
  • the reservoir has at least one inlet allowing the filling of ammonia, from a carboy for example. It can also have an outlet, allowing a filling under ammonia sweep possibly diluted. If necessary, the tank can be purged of ammonia by pulling under vacuum, or under the effect of a gas flow.
  • the present invention also relates to a reservoir as described above and containing the solid as described above. It also relates to such a reservoir further comprising at least one active element as described above.
  • the present invention also relates to a method for the storage of ammonia using a reservoir as described above.
  • the figure 1 illustrates a partitioned tank in cells (1) of identical sections.
  • the cells are dimensioned so that reagents (not shown) can be inserted therein.
  • the walls (2) of the cells are profiled so as to have good resistance to the generation of pressure and to the evacuation. In the example shown, the walls consist of segments of sinusoids.
  • the interstices (3) between the cells have recesses (4) which communicate with the external environment and are used for the insertion of heating or cooling elements. They constitute a heat exchange network.
  • a curved lid (not shown) is fixed above the cells; it comprises a network of pipes (5) which reinforce the structure of the whole. These pipes communicate with the interior of the cells by orifices (6).
  • the lid is assembled in a completely sealed manner on the outer periphery of the tank. The assembly between the lid and the walls of the cells internal to the tank can be made partially or completely sealed.
  • the lid has at least one inlet (7) for filling ammonia, for example from a carboy.
  • the reservoir may have an outlet, allowing a swept filling of ammonia possibly diluted. If necessary, the tank can be purged of ammonia by pulling under vacuum, or under the effect of a gas flow.
  • Secondary chambers (8) arranged laterally in this example, make it possible to reinforce the structure. They can be filled with materials to phase change whose objective is to facilitate the thermal management of the system.
  • the pipes (5) of the cover can be extended by pipes (5 bis) on the side faces of the cells and join similar pipes in the tank bottom, thus providing additional reinforcement (see right version of the Fig. 1 ).
  • the figure 2 illustrates an arrangement of the cells (this time represented with their solid container) providing greater flexibility of shape to the tank.
  • the cells (1a), (1b), (1c), (1d) are offset by an angle ( ⁇ ) (9) which makes it possible to profile the reservoir along the curve (10).
  • the angle ⁇ can be variable from one cell to another, resulting in different relative orientations of the cells.
  • the inter-cell volumes (4) may be filled with phase change materials. They can also be used to set up heating and cooling systems. These volumes may also present (a location for) reinforcement elements of the tank structure.
  • the figure 3 shows (in two sections in vertical planes perpendicular to each other) another possibility of partitioning the reagents (11), in a reservoir injected in two or more pieces (4 cells (1) made separately in fact).
  • a pre-preg material pre-impregnated composite fibers
  • the tank After assembling the four cells (1) comprising the saturated ammonia solid (11), the tank is sealed with a lid (12) held by a flange (13).
  • the lid (12) is equipped with an inlet / outlet port (7) for ammonia flow.
  • the reservoir comprises a hollow profile (14) inserted between the cells (1) and which serves as a housing for a heating element (15), which is thus outside the envelope.
  • the reservoir is reinforced by internal walls and ribs (16) which can be provided with thermally conductive fins. Reinforcing ribs may also be disposed on the outer shell.
  • the figure 4 shows (in two sections in vertical planes perpendicular to each other) an injection-molded cell (1) having a hollow channel (14) for accommodating a heating element (15).
  • the heating element (15) can be easily extracted and replaced by a cooling element (in order to promote the adsorption of the ammonia), since these elements are not sealed to the wall of the cell (1).
  • the inner wall of the cell (1) is provided with ribs (17) promoting the passage of gases between the wall and the reagent (11); this passage also limits the heat losses to the outside of the cell (1).
  • the tank may be surrounded by a double wall (not shown) creating a volume that can act as a heat exchanger. This volume can also be filled by a phase change material.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Sorption Type Refrigeration Machines (AREA)

Abstract

The container comprises cells (1) that communicate with each other and are provided with openings (4) communicating with an outside. The cells contain a solid intended for ammonia sorption. The cells have same form, and are made in one piece by plastic injection and realized separately by injection or blowing of plastic. A portion of the cells are surmounted by a pipeline network (5) for ensuring the communication between the cells. The cells are gathered under a common lid, and delimit with an upper face. The openings communicate with a hollow cavity of the cells. The container comprises cells (1) that communicate with each other and are provided with openings (4) communicating with an outside. The cells contain a solid intended for ammonia sorption. The cells have same form, and are made in one piece by plastic injection and realized separately by injection or blowing of plastic. A portion of the cells are surmounted by a pipeline network (5) for ensuring the communication between the cells. The cells are gathered under a common lid, and delimit with an upper face. The openings communicate with a hollow cavity of the cells. The lid includes an opening ensuring the communication of the cavity with the outside of the container. A shape of the portion of the cells is such that an active element of a system is inserted into or between cells. The cells are equipped with channels to place an active element of a system. The channels are separated in a watertight manner from the cavity of the cells. The active element is a heater, a phase shift material or a cooling element. An inner wall of the cells is provided with ribs. The container further includes an input and an output.

Description

L'invention concerne un réservoir pour le stockage d'ammoniac par sorption, de préférence par chimisorption sur un solide.The invention relates to a tank for the storage of ammonia by sorption, preferably by chemisorption on a solid.

Les oxydes d'azote présents dans les gaz d'échappement des véhicules, notamment Diesel, peuvent être éliminés par la technique de réduction catalytique sélective (généralement appelée SCR ou «Sélective Catalytic Reduction»). Dans ce procédé, des doses d'ammoniac sont injectées dans la ligne d'échappement en amont d'un catalyseur sur lequel les réactions de réduction ont lieu. Actuellement, l'ammoniac est produit par décomposition thermique d'un précurseur, généralement une solution aqueuse d'urée. Des systèmes embarqués de stockage, distribution et dosage d'une solution d'urée normalisée (telle que celle commercialisée sous la dénomination Adblue®, solution eutectique à 32.5% d'urée dans l'eau) ont ainsi été mis sur le marché.Nitrogen oxides present in vehicle exhaust gases, particularly diesel, can be removed by the selective catalytic reduction technique (commonly referred to as SCR or Selective Catalytic Reduction). In this process, doses of ammonia are injected into the exhaust line upstream of a catalyst on which the reduction reactions take place. Currently, ammonia is produced by thermal decomposition of a precursor, usually an aqueous solution of urea. Embedded systems for storing, dispensing and dosing a standard urea solution (such as that sold under the name Adblue®, a eutectic solution containing 32.5% urea in water) have thus been placed on the market.

Une autre technologie consiste à stocker l'ammoniac par sorption sur un sel, le plus souvent un chlorure de métal alcalino-terreux. L'activation thermique permet alors de restituer l'ammoniac dans la phase de fonctionnement du véhicule. Une pression d'ammoniac est donc générée. Ainsi apparaît-il nécessaire de disposer d'un système visant à remplir les différentes fonctionnalités rattachées à cette technologie dans le cas d'une application sur véhicules. Les systèmes actuels, à l'état de prototypes, font appel à un réservoir de stockage cylindrique en acier inoxydable, avec un chauffage en périphérie.Another technology is to store ammonia by sorption on a salt, most often an alkaline earth metal chloride. The thermal activation then makes it possible to restore the ammonia in the operating phase of the vehicle. An ammonia pressure is generated. Thus it appears necessary to have a system to fill the various features associated with this technology in the case of an application on vehicles. Current prototype systems use a cylindrical stainless steel storage tank with peripheral heating.

La demande US 2010/0062296 propose un système de stockage d'ammoniac par chimisorption impliquant au moins deux réservoirs ou compartiments d'un même réservoir contenant des matériaux absorbants différents et ayant des tailles différentes, ces réservoirs/compartiments communiquant pour permettre le passage d'ammoniac entre eux. Une fois le système épuisé en ammoniac, le plus grand d'entre eux (généralement celui qui sert de réserve au plus petit) est remplacé.Requirement US 2010/0062296 proposes a chemisorption ammonia storage system involving at least two tanks or compartments of the same tank containing different absorbent materials and having different sizes, these reservoirs / compartments communicating to allow the passage of ammonia between them. Once the system is depleted of ammonia, the largest of these (usually the one that serves as a reserve for the smallest) is replaced.

La présente invention vise à fournir un réservoir pour le stockage d'ammoniac par sorption, qui est aisé à fabriquer, dont la forme peut facilement être adaptée à son environnement sur un véhicule et qui peut aisément être rechargé en ammoniac au lieu d'être remplacé au moins partiellement.The present invention aims to provide a storage tank for ammonia sorption, which is easy to manufacture, whose shape can easily be adapted to its environment on a vehicle and which can easily be recharged with ammonia instead of being replaced at least partially.

A cet effet, l'invention concerne un réservoir pour le stockage d'ammoniac par sorption, ledit réservoir comprenant des alvéoles communiquant entre elles et avec au moins un orifice communiquant avec l'extérieur, ces alvéoles étant aptes à contenir un solide destiné à la sorption d'ammoniac.To this end, the invention relates to a tank for the storage of ammonia by sorption, said tank comprising cells communicating with each other and with at least one orifice communicating with the outside, these cells being able to contain a solid intended for the ammonia sorption.

Par « réservoir », on entend désigner un récipient ou enceinte délimitant au moins un volume interne servant de contenant au solide. Selon l'invention, le réservoir comprend au moins une paroi délimitant des alvéoles c.à.d. des cavités susceptibles de contenir ledit solide. Ces cavités peuvent avoir une forme quelconque. De préférence, elles ont toutes la même forme.By "reservoir" is meant a container or enclosure defining at least one internal volume serving as a container for the solid. According to the invention, the reservoir comprises at least one wall delimiting cavities, i.e. cavities capable of containing said solid. These cavities may have any shape. Preferably, they all have the same shape.

Selon l'invention, le solide est destiné à la sorption (de préférence, à la chimisorption) d'ammoniac. La demande US susmentionnée décrit et liste de tels solides, et son contenu est à cet effet incorporé dans la présente demande. Il s'agit généralement de chlorures de métaux alcalins, alcalino-terreux ou de transition. Ces solides peuvent être à l'état pulvérulent ou sous forme d'agglomérats. De manière préférée, il y a un agglomérat par alvéole. La forme et la taille des alvéoles sont de préférence adaptées pour pouvoir épouser au moins une partie de la surface externe des agglomérats.According to the invention, the solid is intended for the sorption (preferably chemisorption) of ammonia. The aforementioned US application describes and lists such solids, and its contents are to this effect incorporated in the present application. These are usually alkali metal, alkaline earth or transition metal chlorides. These solids can be in the powdery state or in the form of agglomerates. Preferably, there is one agglomerate per cell. The shape and size of the cells are preferably adapted to fit at least a portion of the outer surface of the agglomerates.

De préférence, les alvéoles sont en matière plastique. Les matières thermoplastiques donnent de bons résultats dans le cadre de l'invention, notamment en raison des avantages de poids, de résistance mécanique et chimique et de mise en oeuvre facilitée (ce qui permet justement d'obtenir des formes complexes).Preferably, the cells are made of plastic. Thermoplastic materials give good results in the context of the invention, in particular because of the advantages of weight, mechanical and chemical resistance and easier implementation (which makes it possible to obtain complex shapes).

En particulier, on peut utiliser des polyoléfines, des polyhalogénures de vinyle, des polyesters thermoplastiques, des polycétones, des polyamides, des polyphtalamides et leurs copolymères. Un mélange de polymères ou de copolymères peut aussi être utilisé, de même qu'un mélange de matières polymériques avec des charges inorganiques, organiques et/ou naturelles comme, par exemple, mais non limitativement : le carbone, les sels et autres dérivés inorganiques, les fibres naturelles, les fibres de verre et les fibres polymériques. Il est également possible d'utiliser des structures multicouches constituées de couches empilées et solidaires comprenant au moins un des polymères ou copolymères décrits supra.In particular, it is possible to use polyolefins, polyvinyl halides, thermoplastic polyesters, polyketones, polyamides, polyphthalamides and their copolymers. A mixture of polymers or copolymers may also be used, as well as a mixture of polymeric materials with inorganic, organic and / or natural fillers such as, for example, but not limited to: carbon, salts and other inorganic derivatives, natural fibers, glass fibers and polymeric fibers. It is also possible to use multilayer structures consisting of stacked and solid layers comprising at least one of the polymers or copolymers described above.

D'excellents résultats ont été obtenus avec du polyphtalamide chargé en fibres de verre.Excellent results have been obtained with polyphthalamide loaded with glass fibers.

Les alvéoles du réservoir selon l'invention peuvent au moins en partie être réalisées d'un seul tenant, par exemple sous forme de plaque(s) injectées. De préférence, une plaque inférieure comprenant des segments de sinusoïdes est assemblée avec une plaque supérieure de forme bombée.The cells of the tank according to the invention may at least partly be made in one piece, for example in the form of plate (s) injected. Of Preferably, a bottom plate comprising sinusoid segments is assembled with a domed top plate.

Des renforts latéraux sous forme de nervures peuvent être ajoutés afin d'améliorer la résistance mécanique des alvéoles.Side reinforcements in the form of ribs may be added to improve the mechanical strength of the cells.

Alternativement, les alvéoles peuvent être réalisées séparément (individuellement ou par groupes), par exemple par injection ou soufflage de matière plastique, puis assemblées par tout moyen connu, tel que par soudure par exemple. Cette variante permet de réaliser un assemblage non parallèle des alvéoles c.à.d. tel qu'avec des alvéoles de forme identique, au moins une des faces desdites alvéoles n'est pas parallèle à la face analogue de sa voisine.Alternatively, the cells may be made separately (individually or in groups), for example by injection or blowing of plastic material, and then assembled by any known means, such as by welding, for example. This variant makes it possible to perform a non-parallel assembly of the cells, ie. such that with cells of identical shape, at least one of the faces of said cells is not parallel to the similar face of its neighbor.

La production de groupes d'alvéoles par injection est particulièrement avantageuse car elle permet notamment de réaliser de manière économique de très petites alvéoles. Or les alvéoles de petite taille permettent d'obtenir une bonne tenue de celles-ci à la (dé)pression interne, et permettent d'améliorer l'échange thermique entre les systèmes de chauffe et/ou de refroidissement et le réactif.The production of groups of cells by injection is particularly advantageous because it makes it possible in particular to economically produce very small cells. However, the small cells allow to obtain a good resistance of these to the (de) internal pressure, and improve the heat exchange between the heating and / or cooling systems and the reagent.

Selon l'invention, les alvéoles communiquent entre elles de sorte à assurer la circulation d'ammoniac tant lors du remplissage (recharge) du réservoir que lors de son utilisation (consommation ou décharge d'ammoniac). Cette communication est généralement assurée par au moins un orifice dans chaque alvéole et par un dispositif reliant ces orifices entre eux et vers au moins un orifice communiquant avec l'extérieur du réservoir, de sorte à permettre sa recharge et sa décharge en ammoniac.According to the invention, the cells communicate with each other so as to ensure the circulation of ammonia both during the filling (refilling) of the reservoir and during its use (consumption or discharge of ammonia). This communication is generally provided by at least one orifice in each cell and by a device connecting these orifices to each other and to at least one orifice communicating with the outside of the tank, so as to allow its recharging and discharge ammonia.

Dans une variante, l'ensemble des alvéoles ou un sous-groupe d'entre elles est surmonté par un réseau de canalisations assurant la communication entre elles. Cette variante est particulièrement avantageuse dans le cas où les alvéoles sont réalisées à partir d'au moins une feuille/plaque soudée localement pour former les alvéoles. Dans cette variante, ledit réseau assure aussi généralement un rôle de renfort mécanique, augmentant la résistance mécanique et la résistance à la (dé)pression du réservoir. Dans cette variante, le réseau peut être libre mais de préférence, il est solidaire d'un couvercle recouvrant les alvéoles et jouant un rôle de renfort supplémentaire.In a variant, all the cells or a subgroup of them is surmounted by a network of pipes providing communication between them. This variant is particularly advantageous in the case where the cells are made from at least one sheet / plate welded locally to form the cells. In this variant, said network also generally performs a role of mechanical reinforcement, increasing the mechanical resistance and resistance to (de) pressure of the reservoir. In this variant, the network may be free but preferably it is secured to a cover covering the cells and playing a role of additional reinforcement.

Dans une autre variante, éventuellement combinable avec la précédente, les alvéoles sont regroupées sous un couvercle commun, délimitant avec leur face supérieure, un volume creux et chaque alvéole comprend au moins un orifice communiquant avec ce volume, le couvercle comprenant au moins un orifice assurant la communication de ce volume avec l'extérieur du réservoir. Dans cette variante, le couvercle peut également avoir pour rôle d'assembler les alvéoles (de les rendre solidaires mécaniquement) et/ou de renforcer le réservoir.In another variant, possibly combinable with the preceding one, the cells are grouped together under a common lid, delimiting with their upper face a hollow volume and each cell comprises at least one orifice communicating with this volume, the lid comprising at least one orifice ensuring the communication of this volume with the outside of the tank. In this variant, the cover may also serve to assemble the cells (to make them mechanically integral) and / or to reinforce the reservoir.

De préférence, la forme des alvéoles (toutes ou partie d'entre elles) et/ou leur mode de réalisation et/ou d'assemblage est tel qu'au moins un élément actif du système (remplissant une fonction utile telle que chauffage, refroidissement ou renfort mécanique) puisse être inséré dans ou entre elles. Par exemple, un élément chauffant ou un matériau à changement de phase (MCP, ou matériau stockant ou restituant de la chaleur en changeant de phase selon la température qui l'environne) est avantageusement inséré dans ou entre les alvéoles.Preferably, the shape of the cells (all or part of them) and / or their embodiment and / or assembly is such that at least one active element of the system (fulfilling a useful function such as heating, cooling or mechanical reinforcement) can be inserted into or between them. For example, a heating element or a phase change material (MCP, or material storing or returning heat by changing phase according to the surrounding temperature) is advantageously inserted in or between the cells.

L'usage d'éléments chauffants ou de matériaux à changement de phase permet de stabiliser la température du réactif contenu dans l'alvéole et d'assurer ainsi une production stable d'ammoniac. De plus, l'utilisation de chauffe différenciée entre alvéoles et/ou de quantités relatives différentes de matériaux à changement de phase entre alvéoles permet d'appauvrir ou d'enrichir certaines alvéoles en ammoniac; par exemple, lors d'un arrêt du système (suite par exemple à un arrêt du véhicule), la charge en ammoniac dans les alvéoles refroidissant plus vite (contenant par exemple peu ou pas de matériau à changement de phase) augmentera au détriment des alvéoles refroidissant plus lentement (contenant par exemple beaucoup de matériau à changement de phase). Ceci peut être particulièrement intéressant pour assurer une mise à disposition rapide d'ammoniac après un arrêt du véhicule, par exemple en activant à ce moment préférentiellement les alvéoles riches en ammoniac.The use of heating elements or phase change materials makes it possible to stabilize the temperature of the reagent contained in the cell and thus ensure a stable production of ammonia. In addition, the use of differentiated heating between cells and / or different relative amounts of phase change materials between cells allows to deplete or enrich some cells to ammonia; for example, during a shutdown of the system (following for example a stopping of the vehicle), the ammonia load in the cells cooling faster (containing for example little or no phase change material) will increase to the detriment of the cells cooling more slowly (containing for example a lot of phase change material). This may be particularly advantageous to ensure rapid availability of ammonia after stopping the vehicle, for example by activating at this time preferably ammonia-rich cells.

Les alvéoles peuvent également être traversées ou pénétrées, de préférence dans leur plus grande dimension, par un ou plusieurs canaux éventuellement obturés à l'une de leurs extrémités et qui permet également l'insertion d'un élément actif du système. Cette disposition est particulièrement favorable pour le positionnement de moyens de chauffe ou de refroidissement: les canaux étant placés substantiellement au centre du réactif permettent des échanges thermiques rapides. De plus, si le logement interne des canaux est séparé des réactifs par la paroi (en d'autres termes: si les canaux sont séparés de manière étanche du volume interne des alvéoles), les moyens de chauffe ou de refroidissement qui y sont positionnés ne doivent pas être attachés de manière étanche. Ceci permet en particulier de les démonter facilement, et de monter alternativement dans ces canaux des moyens de chauffe (lors de la désorption de l'ammoniac) ou de refroidissement (lors de l'absorption d'ammoniac).The cells may also be traversed or penetrated, preferably in their largest dimension, by one or more channels optionally closed at one of their ends and which also allows the insertion of an active element of the system. This arrangement is particularly favorable for the positioning of heating or cooling means: the channels being placed substantially in the center of the reagent allow rapid heat exchange. In addition, if the internal housing of the channels is separated from the reagents by the wall (in other words: if the channels are sealed from the internal volume of the cells), the heating or cooling means which are positioned therein must not be attached tightly. This makes it possible in particular to dismount them easily, and to alternately mount in these channels heating means (during the desorption of ammonia) or cooling (during the absorption of ammonia).

De bons résultats ont été obtenus lorsque le nombre de canaux sur l'ensemble des alvéoles est supérieur à 1 canal par 4 litres de réactif; c'est tout particulièrement le cas lorsque ce nombre dépasse 1 par litre de réactif.Good results have been obtained when the number of channels on all the cells is greater than 1 channel per 4 liters of reagent; this is particularly the case when this number exceeds 1 per liter of reagent.

Les moyens de chauffe et/ou MCP, ainsi que les moyens de refroidissement peuvent être placés tant dans des canaux internes qu'à l'extérieur des alvéoles, voire même en ce qui concerne les MCP à l'intérieur des alvéoles, dans la chambre du réactif. Une combinaison particulièrement intéressante est de placer les moyens de chauffe dans des canaux tels que décrits précédemment et les MCP à l'extérieur des alvéoles, éventuellement surmontés de moyens d'isolation ; cette configuration permet en effet d'obtenir de bonnes performances dynamiques du système de chauffe: en cas de démarrage dans des conditions froides, la chaleur générée à l'intérieur des canaux est en effet très rapidement transmise au réactif, car l'enthalpie nécessaire à la chauffe des canaux est faible vu leurs petites dimensions et leurs faibles masses. Les MCP placés à l'extérieur des alvéoles ne se mettent à chauffer qu'après que le lit de réactif soit chauffé et permettent de récupérer la chaleur arrivant en périphérie et de stabiliser la température des réactifs et la pression d'ammoniac. Les MCP placés à l'extérieur jouent de plus un effet isolant, complémentaire à celui joué par les isolants qui peuvent être placés en couche externe au-dessus des MCP.The heating means and / or MCP, as well as the cooling means can be placed both in internal channels and outside the cells, or even with regard to the MCP inside the cells, in the chamber reagent. A particularly interesting combination is to place the heating means in channels as described above and the MCP outside the cells, possibly topped with isolation means; this configuration makes it possible to obtain good dynamic performance of the heating system: when starting in cold conditions, the heat generated inside the channels is indeed very quickly transmitted to the reagent, because the enthalpy needed to the heating of the channels is weak because of their small dimensions and their small masses. The MCPs placed outside the cells do not start heating until the reagent bed is heated and allow the heat to be recovered at the periphery and to stabilize the reagent temperature and the ammonia pressure. Outdoor PCMs also have an insulating effect, complementary to that of insulators that can be placed in an outer layer above PCMs.

Dans une variante particulièrement intéressante de l'invention, le réservoir comprend un MCP dans au moins une partie des alvéoles et/ou entre au moins une partie d'entre elles et/ou dans un canal isolant d'au moins une partie d'entre elles.In a particularly advantageous variant of the invention, the reservoir comprises a MCP in at least a portion of the cells and / or between at least part of them and / or in an insulating channel of at least a part of they.

Les parois des alvéoles peuvent être munies de nervures internes permettant un bon passage des gaz entre les réactifs et les parois. Ce passage permet également de limiter les pertes de chaleur vers l'extérieur du dispositif.The walls of the cells may be provided with internal ribs allowing good gas passage between the reagents and the walls. This passage also limits heat loss to the outside of the device.

Dans une variante de l'invention, le réservoir présente au moins une entrée permettant le remplissage d'ammoniac, à partir d'une bonbonne par exemple. Il peut également présenter une sortie, permettant un remplissage sous balayage d'ammoniac éventuellement dilué. Si nécessaire, le réservoir peut être purgé de l'ammoniac en tirant sous vide, ou sous l'effet d'un flux gazeux.In a variant of the invention, the reservoir has at least one inlet allowing the filling of ammonia, from a carboy for example. It can also have an outlet, allowing a filling under ammonia sweep possibly diluted. If necessary, the tank can be purged of ammonia by pulling under vacuum, or under the effect of a gas flow.

La présente invention concerne également un réservoir tel que décrit ci-dessus et contenant le solide tel que décrit ci-dessus. Elle concerne également un tel réservoir comprenant en outre au moins un élément actif tel que décrit ci-dessus.The present invention also relates to a reservoir as described above and containing the solid as described above. It also relates to such a reservoir further comprising at least one active element as described above.

Enfin, la présente invention concerne également un procédé pour le stockage d'ammoniac utilisant un réservoir tel que décrit ci-dessus.Finally, the present invention also relates to a method for the storage of ammonia using a reservoir as described above.

L'invention est illustrée de manière non limitative par les figures 1 à 3 en annexe, qui en illustrent de manière schématique:

  • Fig. 1: une vue du dessus d'un réservoir selon une 1ère variante de l'invention
  • Fig. 2: une vue en coupe par un plan vertical d'un réservoir selon une 2ème variante de l'invention
  • Fig. 3: deux vues en coupe selon des plans verticaux perpendiculaires entre eux, d'un réservoir selon une 3ème variante de l'invention.
The invention is illustrated in a non-limiting way by the Figures 1 to 3 in the appendix, which illustrates in a schematic way:
  • Fig. 1 : A top view of a tank according to a 1st embodiment of the invention
  • Fig. 2 Is a view in section through a vertical plane of a tank according to a 2nd embodiment of the invention
  • Fig. 3 Two sectional views along vertical planes perpendicular to each other, a reservoir according to a 3rd embodiment of the invention.

Dans ces figures, des n° identiques désignent des éléments identiques ou similaires.In these figures, identical numbers designate identical or similar elements.

La figure 1 illustre un réservoir partitionné en alvéoles (1) de sections identiques. Les alvéoles sont dimensionnées de manière à ce que des réactifs (non représentés) puissent y être insérés. Les parois (2) des alvéoles sont profilées de façon à présenter une bonne résistance à la génération de pression et à la mise sous vide. Dans l'exemple représenté, les parois sont constituées de segments de sinusoïdes. Les interstices (3) entre les alvéoles présentent des évidements (4) qui communiquent avec l'environnement extérieur et sont mis à profit pour l'insertion d'éléments chauffants ou de refroidissement. Ils constituent un réseau d'échange de chaleur.The figure 1 illustrates a partitioned tank in cells (1) of identical sections. The cells are dimensioned so that reagents (not shown) can be inserted therein. The walls (2) of the cells are profiled so as to have good resistance to the generation of pressure and to the evacuation. In the example shown, the walls consist of segments of sinusoids. The interstices (3) between the cells have recesses (4) which communicate with the external environment and are used for the insertion of heating or cooling elements. They constitute a heat exchange network.

Un couvercle de forme bombée (non représenté) est fixé au dessus des alvéoles; il comprend un réseau de canalisations (5) qui viennent renforcer la structure de l'ensemble. Ces canalisations communiquent avec l'intérieur des alvéoles par des orifices (6). Le couvercle est assemblé de manière totalement étanche sur la périphérie externe du réservoir. L'assemblage entre le couvercle et les parois des alvéoles internes au réservoir peut être réalisé de manière partiellement ou totalement étanche.A curved lid (not shown) is fixed above the cells; it comprises a network of pipes (5) which reinforce the structure of the whole. These pipes communicate with the interior of the cells by orifices (6). The lid is assembled in a completely sealed manner on the outer periphery of the tank. The assembly between the lid and the walls of the cells internal to the tank can be made partially or completely sealed.

Le couvercle présente au moins une entrée (7) permettant le remplissage d'ammoniac, à partir d'une bonbonne par exemple.The lid has at least one inlet (7) for filling ammonia, for example from a carboy.

Dans une variante de cet exemple, le réservoir peut présenter une sortie, permettant un remplissage sous balayage d'ammoniac éventuellement dilué. Si nécessaire, le réservoir peut être purgé de l'ammoniac en tirant sous vide, ou sous l'effet d'un flux gazeux.In a variant of this example, the reservoir may have an outlet, allowing a swept filling of ammonia possibly diluted. If necessary, the tank can be purged of ammonia by pulling under vacuum, or under the effect of a gas flow.

Des chambres secondaires (8), disposées latéralement dans cet exemple, permettent de renforcer la structure. Elles peuvent être remplies de matériaux à changement de phase dont l'objectif est de faciliter la gestion thermique du système.Secondary chambers (8), arranged laterally in this example, make it possible to reinforce the structure. They can be filled with materials to phase change whose objective is to facilitate the thermal management of the system.

A noter que les canalisations (5) du couvercle peuvent se prolonger par des canalisations (5 bis) sur les faces latérales des alvéoles et rejoindre des canalisations similaires dans le fond du réservoir, assurant ainsi un renfort supplémentaire (voir version de droite de la Fig. 1).Note that the pipes (5) of the cover can be extended by pipes (5 bis) on the side faces of the cells and join similar pipes in the tank bottom, thus providing additional reinforcement (see right version of the Fig. 1 ).

La figure 2 illustre une disposition des alvéoles (cette fois-ci représentées avec leur contenant solide) offrant une plus grande flexibilité de forme au réservoir. Les alvéoles (1a), (1b), (1c), (1d) sont décalées d'un angle (α) (9) ce qui permet de profiler le réservoir suivant la courbe (10).The figure 2 illustrates an arrangement of the cells (this time represented with their solid container) providing greater flexibility of shape to the tank. The cells (1a), (1b), (1c), (1d) are offset by an angle (α) (9) which makes it possible to profile the reservoir along the curve (10).

L'angle α peut être variable d'une alvéole à l'autre, résultant en des orientations relatives différentes des alvéoles. Les volumes (4) inter alvéoles peuvent être garnis de matériaux à changement de phase. Ils peuvent aussi servir à la mise en place de systèmes de réchauffage et de refroidissement. Ces volumes peuvent également présenter (un emplacement pour) des éléments de renfort de la structure du réservoir.The angle α can be variable from one cell to another, resulting in different relative orientations of the cells. The inter-cell volumes (4) may be filled with phase change materials. They can also be used to set up heating and cooling systems. These volumes may also present (a location for) reinforcement elements of the tank structure.

La figure 3 montre (en deux coupes selon des plans verticaux perpendiculaires entre eux) une autre possibilité de partitionnement des réactifs (11), dans un réservoir injecté en deux ou plusieurs pièces (4 alvéoles (1) réalisées séparément en fait). Un matériau pre-preg (fibres composites pré-imprégnées) peut être utilisé pour la fabrication du réservoir.The figure 3 shows (in two sections in vertical planes perpendicular to each other) another possibility of partitioning the reagents (11), in a reservoir injected in two or more pieces (4 cells (1) made separately in fact). A pre-preg material (pre-impregnated composite fibers) can be used for the manufacture of the tank.

Après assemblage des quatre alvéoles (1) comprenant le solide saturé en ammoniac (11), le réservoir est fermé de manière étanche avec un couvercle (12) maintenu par une bride (13). Le couvercle (12) est équipé d'un orifice entré/sortie (7) pour le débit d'ammoniac. Le réservoir comprend un profilé creux (14) inséré entre les alvéoles (1) et qui sert de logement à un élément chauffant (15), qui est ainsi à l'extérieur de l'enveloppe. Le réservoir est renforcé par des parois et nervures internes (16) qui peuvent être munies d'ailettes thermiquement conductrices. Des nervures de renfort peuvent être également disposées sur l'enveloppe externe.After assembling the four cells (1) comprising the saturated ammonia solid (11), the tank is sealed with a lid (12) held by a flange (13). The lid (12) is equipped with an inlet / outlet port (7) for ammonia flow. The reservoir comprises a hollow profile (14) inserted between the cells (1) and which serves as a housing for a heating element (15), which is thus outside the envelope. The reservoir is reinforced by internal walls and ribs (16) which can be provided with thermally conductive fins. Reinforcing ribs may also be disposed on the outer shell.

La figure 4 montre (en deux coupes selon des plans verticaux perpendiculaires entre eux) une alvéole (1) moulée par injection comportant un canal creux (14) permettant de loger un élément chauffant (15). Lors de la recharge en ammoniac, l'élément chauffant (15) peut être aisément extrait et remplacé par un élément réfrigérant (en vue de favoriser l'adsorption de l'ammoniac), vu que ces éléments ne sont pas fixés de manière étanche sur la paroi de l'alvéole (1). La paroi interne de l'alvéole (1) est munie de nervures (17) favorisant le passage des gaz entre la paroi et le réactif (11) ; ce passage limite également les déperditions calorifiques vers l'extérieur de l'alvéole (1).The figure 4 shows (in two sections in vertical planes perpendicular to each other) an injection-molded cell (1) having a hollow channel (14) for accommodating a heating element (15). When recharging with ammonia, the heating element (15) can be easily extracted and replaced by a cooling element (in order to promote the adsorption of the ammonia), since these elements are not sealed to the wall of the cell (1). The inner wall of the cell (1) is provided with ribs (17) promoting the passage of gases between the wall and the reagent (11); this passage also limits the heat losses to the outside of the cell (1).

Le réservoir peut être entouré par une double paroi (non représentée) créant un volume pouvant jouer le rôle d'échangeur thermique. Ce volume peut également être rempli par un matériau à changement de phase.The tank may be surrounded by a double wall (not shown) creating a volume that can act as a heat exchanger. This volume can also be filled by a phase change material.

Claims (15)

Réservoir pour le stockage d'ammoniac par sorption, ledit réservoir comprenant des alvéoles communiquant entre elles et avec au moins un orifice communiquant avec l'extérieur, ces alvéoles étant aptes à contenir un solide destiné à la sorption d'ammoniac.A tank for the storage of ammonia by sorption, said tank comprising cells communicating with each other and with at least one orifice communicating with the outside, these cells being able to contain a solid intended for the sorption of ammonia. Réservoir selon la revendication précédente, dans lequel les alvéoles ont toutes la même forme.Tank according to the preceding claim, wherein the cells all have the same shape. Réservoir selon l'une quelconque des revendications précédentes, dans lequel les alvéoles sont au moins en partie réalisées d'un seul tenant par injection de matière plastique.Tank according to any one of the preceding claims, wherein the cells are at least partly made in one piece by plastic injection. Réservoir selon la revendication 1 ou 2, dans lequel les alvéoles sont réalisées séparément (individuellement ou par groupes), par injection ou soufflage de matière plastique, puis assemblées.Tank according to claim 1 or 2, wherein the cells are made separately (individually or in groups), by injection or blowing of plastic, and then assembled. Réservoir selon l'une quelconque des revendications précédentes, dans lequel au moins une partie des alvéoles sont surmontées par un réseau de canalisations assurant la communication entre elles.Tank according to any one of the preceding claims, wherein at least a portion of the cells are surmounted by a network of pipes providing communication between them. Réservoir selon l'une quelconque des revendications précédentes, dans lequel les alvéoles sont regroupées sous un couvercle commun, délimitant avec leur face supérieure, un volume creux et dans lequel chaque alvéole comprend au moins un orifice communiquant avec ce volume, le couvercle comprenant au moins un orifice assurant la communication de ce volume avec l'extérieur du réservoir.Tank according to any one of the preceding claims, in which the cells are grouped together under a common lid, delimiting with their upper face a hollow volume and in which each cell comprises at least one orifice communicating with this volume, the lid comprising at least an orifice ensuring the communication of this volume with the outside of the tank. Réservoir selon l'une quelconque des revendications précédentes, dans lequel la forme d'au moins une partie des alvéoles et/ou leur mode de réalisation et/ou d'assemblage est tel qu'au moins un élément actif du système puisse être inséré dans ou entre elles.Tank according to any one of the preceding claims, in which the shape of at least part of the cells and / or their embodiment and / or assembly is such that at least one active element of the system can be inserted into or between them. Réservoir selon la revendication précédente, dans lequel certaines alvéoles sont pourvues d'un ou de plusieurs canaux permettant de loger au moins un élément actif du système.Tank according to the preceding claim, wherein some cells are provided with one or more channels for housing at least one active element of the system. Réservoir selon la revendication précédente, dans lequel les canaux sont séparés de manière étanche du volume interne des alvéoles.Tank according to the preceding claim, wherein the channels are sealed from the internal volume of the cells. Réservoir selon l'une quelconque des revendications 7 à 9, dans lequel l'élément actif est un élément chauffant, un matériau à changement de phase ou un élément réfrigérant.A tank according to any one of claims 7 to 9, wherein the active element is a heating element, a phase change material or a cooling element. Réservoir selon l'une quelconque des revendications 7 à 10, comprenant un matériau à changement de phase dans au moins une partie des alvéoles et/ou entre au moins une partie d'entre elles et/ou dans un canal isolant d'au moins une partie d'entre elles.Tank according to any one of claims 7 to 10, comprising a phase change material in at least a portion of the cells and / or between at least part of them and / or in an insulating channel of at least one part of them. Réservoir selon l'une quelconque des revendications précédentes, dans lequel la paroi interne des alvéoles est munie de nervures.Tank according to any one of the preceding claims, wherein the inner wall of the cells is provided with ribs. Réservoir selon l'une quelconque des revendications précédentes, comprenant au moins une entrée et une sortie.Tank according to any one of the preceding claims, comprising at least one inlet and one outlet. Réservoir selon l'une quelconque des revendications précédentes, dans lequel les alvéoles comprennent un solide destiné à la sorption d'ammoniac.A tank according to any one of the preceding claims, wherein the cells comprise a solid for ammonia sorption. Réservoir selon la revendication précédente, dans lequel le solide est un chlorure de métal alcalin, alcalino-terreux ou de transition.Tank according to the preceding claim, wherein the solid is an alkali metal chloride, alkaline earth or transition.
EP11183413A 2011-09-30 2011-09-30 Container for storing ammonia by sorption Withdrawn EP2574599A1 (en)

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EP11183413A EP2574599A1 (en) 2011-09-30 2011-09-30 Container for storing ammonia by sorption
CN201280050396.XA CN103857624A (en) 2011-09-30 2012-10-01 Tank for storing ammonia by sorption
PCT/EP2012/069342 WO2013045696A1 (en) 2011-09-30 2012-10-01 Tank for storing ammonia by sorption
EP12778644.0A EP2760792A1 (en) 2011-09-30 2012-10-01 Tank for storing ammonia by sorption
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WO2014147335A1 (en) 2013-03-18 2014-09-25 Inergy Automotive Systems Research (Société Anonyme) Selective catalytic reduction pollution-control system
ITBO20130370A1 (en) * 2013-07-16 2015-01-17 Magneti Marelli Spa SOLID TANK COLLECTION TANK TO STORE AMMONIA FOR A DISCHARGE SYSTEM PROVIDED WITH POST-TREATMENT OF EXHAUST GASES IN AN INTERNAL COMBUSTION ENGINE

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EP2760792A1 (en) 2014-08-06
CN103857624A (en) 2014-06-11
US20140284224A1 (en) 2014-09-25
WO2013045696A1 (en) 2013-04-04

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